U.S. patent application number 17/681044 was filed with the patent office on 2022-09-01 for additive free fabrication of polymeric composites with delayed and reduced dripping.
The applicant listed for this patent is Ehsan Behzadfar. Invention is credited to Frank S. Bates, Ehsan Behzadfar, Alex M. Jordan, Kyungtae Kim, Christopher W. Macosko.
Application Number | 20220274386 17/681044 |
Document ID | / |
Family ID | 1000006363611 |
Filed Date | 2022-09-01 |
United States Patent
Application |
20220274386 |
Kind Code |
A1 |
Behzadfar; Ehsan ; et
al. |
September 1, 2022 |
ADDITIVE FREE FABRICATION OF POLYMERIC COMPOSITES WITH DELAYED AND
REDUCED DRIPPING
Abstract
Multilayer composite materials are described herein. The
multilayer composite materials have a first layer comprising a
first polymer and a second layer comprising a second polymer. The
first layer and the second layer abut each other. The first layer
and the second layer each have a thickness in a range of about 10
nm to about 1 mm. The first layer and the second layer are arranged
to provide for the multilayer composite material to have reduced
dripping and a delayed first dripping time as they undergo a
combustion process relative to a single layer material having a
same thickness as a thickness of the multilayer composite
materials.
Inventors: |
Behzadfar; Ehsan; (Toronto,
CA) ; Macosko; Christopher W.; (Minneapolis, MN)
; Bates; Frank S.; (Minneapolis, MN) ; Jordan;
Alex M.; (Menomonie, WI) ; Kim; Kyungtae;
(Minneapolis, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Behzadfar; Ehsan |
Toronto |
|
CA |
|
|
Family ID: |
1000006363611 |
Appl. No.: |
17/681044 |
Filed: |
February 25, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63154374 |
Feb 26, 2021 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 27/32 20130101;
B29K 2023/12 20130101; B29C 48/21 20190201; B29C 48/304 20190201;
B32B 27/08 20130101; B32B 2250/04 20130101; B29L 2009/00 20130101;
B32B 2250/05 20130101; B29K 2023/06 20130101 |
International
Class: |
B32B 27/08 20060101
B32B027/08; B32B 27/32 20060101 B32B027/32; B29C 48/21 20060101
B29C048/21; B29C 48/30 20060101 B29C048/30 |
Claims
1. A multilayer composite material comprising: a first layer
comprising a first polymer; and a second layer comprising a second
polymer, the first layer and the second layer abutting each other;
wherein the first layer and the second layer each have a thickness
in a range of about 10 nm to about 1 mm; and the first layer and
the second layer are arranged to provide for the composite material
to have reduced dripping and a delayed first dripping time as the
multilayer composite material undergoes a combustion process
relative to a single layer having a same thickness as a thickness
of the multilayer composite material.
2. The multilayer composite material of claim 1, wherein the
multilayer composite material comprises between two sheets and
about 2500 sheets.
3. The multilayer composite material of claim 1, wherein the
multilayer composite material comprises about 512 layers, or about
640 layers, or about 1520 layers or about 2540 layers.
4. The multilayer composite material of claim 1, wherein the first
polymer and the second polymer are a same polymer.
5. The multilayer composite material of claim 1, wherein the first
polymer and the second polymer are different polymers.
6. The multilayer composite material of claim 5, wherein
alternating layers of the multilayer composite material comprise
the first polymer and the second polymer, respectively.
7. The multilayer composite material of claim 5, further comprising
a third layer comprising a third polymer, the third polymer being
different than the first polymer and the second polymer.
8. The multilayer composite material of claim 7, further comprising
a fourth layer comprising a fourth polymer, the fourth polymer
being different than the first polymer, the second polymer and the
third polymer.
9. The multilayer composite material of claim 1, wherein each of
the layers has a same thickness.
10. The multilayer composite material of claim 1, wherein each of
the layers has a different thickness.
11. The multilayer composite material of claim 1, wherein the
thickness of the multilayer composite material is in a range of
about 0.1 mm to about 3 mm.
12. The multilayer composite material of claim 1, wherein the
thickness of each layer of the multilayer composite material is in
a range of about 10 mm to about 0.1 mm.
13. The multilayer composite material of claim 1, wherein the
thickness of each layer of the composite material is in a range of
about 40 nm to about 0.01 mm.
14. The multilayer composite material of claim 1, wherein the
multilayer composite material has a drip time in a range of about
30 to about 40 s/mm or of about 36 s/mm.
15. The multilayer composite material of claim 1, wherein the
multilayer composite material has a normalized number of drips in a
range of about 100 drips/mm to about 250 drips/mm, or of about 190
drips/mm, or of about 120 drips/mm.
16. The multilayer composite material of claim 1, wherein the first
layer and the second layer are arranged to provide for the
composite material to have an increased extensional viscosity
relative to a single layer having the same thickness as the
thickness of the multilayer composite material.
17. The multilayer composite material of claim 1, wherein the first
layer and the second layer are arranged to provide for an increased
interfacial tension as a temperature of the composite material
increases during the combustion process relative to a single layer
having the same thickness as the thickness of the multilayer
composite material.
18. The multilayer composite material of claim 1, wherein the first
polymer is a polyethylene-based polymer.
19. The multilayer composite material of claim 1, wherein the
second polymer is a polypropylene-based polymer.
20. A method of forming a multilayered composite material, the
method comprising: splitting a first polymer stream into a
plurality of first polymer streams in a feedblock, splitting a
second polymer stream into a plurality of second polymer streams in
a feedblock, combining the plurality of first polymer streams with
the plurality of second polymer streams in an alternating fashion
to form a plurality of discrete, alternating layers; and using a
multiplication die, increasing a number of the alternating layers
to form a multilayer composite material, each layer of the
multilayer composite material having a thickness in a range of 10
nm to 0.5 mm.
Description
CROSS-REFERENCE
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 63/154,374 titled "Additive Free Fabrication
of Polymeric Composites with Delayed and Reduced Dripping" filed on
Feb. 26, 2021, the entire contents of which are incorporated herein
by reference.
FIELD
[0002] This disclosure relates generally to polymer composite
materials, and more specifically to multilayer polymer composite
materials with delayed and reduced dripping.
BACKGROUND
[0003] Performance of polymers in the case of a fire is a critical
factor for consumer safety in buildings and aircraft, and with
protective layers used in construction and packaging
industries..sup.1-9 This performance is dependent on the behavior
of the polymer at different zones in the combustion process, as
illustrated, for example, in FIG. 1A. These zones include the local
degradation, combustion, and char formation zones. During
combustion, polymeric materials melt and flow down to the local
degradation zone where pyrolysis occurs and flammable volatiles are
formed, which fuel the fire. In most polymers, combustion is
accompanied by the formation of a char layer and the release of
toxic fumes.
[0004] To evaluate the response of materials in a combustion
process, two main phenomena are generally considered for
investigation: dripping and flame spread rates (hereafter referred
to as burning rates)..sup.5,19 Dripping indicates the spread of the
fire through the detachment of burning parts of the material while
burning rates refer to the rate of flame advancement throughout the
material. As shown in FIG. 1B, dripping for polymers takes place
due to the capillary breakup of the melt stream and, if ignited,
can carry burning material beyond the sample.
[0005] Dripping is important for the fire safety of products from
two perspectives: (i) first drip time, which is the time required
for the first drop to be disengaged from the fuel bed, and (ii) the
overall number of drips. For example, US federal regulations
dictate that all modern airliners capable of carrying more than 44
passengers must be able to be fully evacuated in less than 90
seconds..sup.11 Any improvement to the first drip time can be
important as it lengthens the critical period at the start of a
fire to sound the alarm, access fire extinguishers, and let more
vulnerable people evacuate the fire area.
[0006] Burning rates for solid materials are defined as the rate of
flame advancement over a solid fuel bed. FIG. 1B depicts a model
that describes the surface flame advancement process..sup.3 In this
representation, h.sub.0 is the thickness of the material, L.sub.p
is the pyrolysis height, {dot over (q)}.sub.f is the net heat flux,
.delta..sub.f is the characteristic length of radiation, L.sub.f is
the flame height, T.sub.f is the temperature of the flame, T.sub.p
is the pyrolysis temperature of the material, and T.sub..infin. is
the ambient temperature. Homopolymer films without any additives
show almost immediate dripping after ignition and generate a high
number of drips..sup.3,12 Nearly all of them also show excessive
burning rates..sup.4,13-17
[0007] To reduce the dripping severity in polymers, anti-dripping
agents are commonly used in the plastic industry.
Polytetrafluoroethylene (PTFE) is a known anti-dripping agent that
forms fibrils in the polymeric matrix, furnishing the material with
increased extensional viscosity..sup.18-22 To counteract the
notoriously flammable nature of polymers, flame retardants are
added to plastic products to delay the flame advancement based on
three main mechanisms: vapor phase inhibition,.sup.13,16 solid
phase char-formation,.sup.14,15,17 and cooling..sup.23 Vapor phase
inhibition takes place once the additives produce components that
react with the burning material in the vapor phase to disrupt the
production of free radicals..sup.13,16 Commonly, this type of
additive consists of halogenated molecules..sup.16 For the
mechanism involving solid phase char-formation, the additives react
to form a carbonaceous char layer that insulates the polymer, which
slows pyrolysis and forms an oxygen barrier layer..sup.14 Additives
with phosphorous and nitrogen chemistries are examples of flame
retardants in this category. Recently, Chu et al..sup.14 used
layers of phosphorous and silicon coatings to improve the barrier
properties of fabric-reinforced polyester composites and hamper the
heat release during the combustion process. Additives such as phase
change materials that undergo an endothermic reaction during
burning promote a cooling mechanism to slow down the combustion
reaction..sup.23
[0008] A plethora of research shows that toxic fumes are released
from anti-dripping and flame retardant additives including
halogenated substances during combustion..sup.24 Shimizu et
al..sup.24 showed that exposure to PTFE fumes renders fever,
dyspnoea, and non-productive coughs, all proven to be originated by
diffuse interstitial infiltration in the lungs. It is worth noting
that environmental safety regulations, such as the Restriction
oazardous Substances Directive (RoHS), promote halogen free
substances, which limits the use of many historically used
additives..sup.25 On the other hand, additives used as
anti-dripping agents and flame retardants are costly and impose
processing challenges such as nonhomogeneous dispersion due to poor
mixing..sup.26,27 Hence, finding a solution that relies on
morphological structures rather than material chemistry is highly
desirable.
[0009] Investigation of the relationship between morphology and
burning rates or dripping in polymers has been limited to filled
polymers..sup.28-30 Kashiwagi et al..sup.28 reported lower burning
rates for polymeric nanocomposites containing carbon nanotube
additives with high aspect ratios. This is due to the formation of
a network structure of nanoparticles in the polymeric matrix that
hinders the pyrolysis reactions and decreases the release rate of
flammable volatiles. In another study, Liu et al..sup.29 reported
that better dispersion of clay decreases the peak mass loss rate of
poly(styrene-co-acrylonitrile) nanocomposites. They showed that
with a stronger network within the polymeric matrix, the bubbling
of released volatiles is suppressed as a protective char layer is
formed under degradation conditions. However, there does not appear
to have been any research investigating the effect of morphological
configurations on dripping and burning rates in unfilled
polymers.
[0010] Accordingly, there is a need for new polymer composite
materials, and more specifically to multilayer polymer composite
materials with delayed and reduced dripping.
SUMMARY
[0011] In accordance with one broad aspect, multilayer composite
materials are described herein. The multilayer composite materials
include a first layer comprising a first polymer and a second layer
comprising a second polymer. The first layer and the second layer
abut each other. The first layer and the second layer each have a
thickness in a range of about 10 nm to about 1 mm. The first layer
and the second layer are arranged to provide for the composite
material to have reduced dripping and a delayed first dripping time
as the multilayer composite material undergoes a combustion process
relative to a single layer having a same thickness as a thickness
of the multilayer composite material.
[0012] In at least one embodiment, the multilayer composite
material comprises between two sheets and about 2500 sheets.
[0013] In at least one embodiment, the multilayer composite
material comprises about 512 layers, or about 640 layers, or about
1520 layers or about 2540 layers.
[0014] In at least one embodiment, the first polymer and the second
polymer are a same polymer.
[0015] In at least one embodiment, the first polymer and the second
polymer are different polymers.
[0016] In at least one embodiment, alternating layers of the
multilayer composite material comprise the first polymer and the
second polymer, respectively.
[0017] In at least one embodiment, the multilayer composite
materials includes a third layer comprising a third polymer, the
third polymer being different than the first polymer and the second
polymer.
[0018] In at least one embodiment, the multilayer composite
materials includes a fourth layer comprising a fourth polymer, the
fourth polymer being different than the first polymer, the second
polymer and the third polymer.
[0019] In at least one embodiment, each of the layers has a same
thickness.
[0020] In at least one embodiment, each of the layers has a
different thickness.
[0021] In at least one embodiment, the thickness of the multilayer
composite material is in a range of about 0.1 mm to about 3 mm.
[0022] In at least one embodiment, the thickness of each layer of
the multilayer composite material is in a range of about 10 mm to
about 0.1 mm.
[0023] In at least one embodiment, the thickness of each layer of
the composite material is in a range of about 40 mm to about 0.01
mm.
[0024] In at least one embodiment, the multilayer composite
material has a drip time in a range of about 30 to about 40 s/mm or
of about 36 s/mm.
[0025] In at least one embodiment, the multilayer composite
material has a normalized number of drips in a range of about 100
drips/mm to about 250 drips/mm, or of about 190 drips/mm, or of
about 120 drips/mm.
[0026] In at least one embodiment, the first layer and the second
layer are arranged to provide for the composite material to have an
increased extensional viscosity relative to a single layer having
the same thickness as the thickness of the multilayer composite
material.
[0027] In at least one embodiment, the first layer and the second
layer are arranged to provide for an increased interfacial tension
as a temperature of the composite material increases during the
combustion process relative to a single layer having the same
thickness as the thickness of the multilayer composite
material.
[0028] In at least one embodiment, the first polymer is a
polyethylene-based polymer.
[0029] In at least one embodiment, the first polymer is a linear
low-density polyethylene-based polymer.
[0030] In at least one embodiment, the second polymer is a
polypropylene-based polymer.
In accordance with another broad aspect, methods of forming
multilayer composite materials are described herein. The methods
include splitting a first polymer stream into a plurality of first
polymer streams in a feedblock, splitting a second polymer stream
into a plurality of second polymer streams in a feedblock,
combining the plurality of first polymer streams with the plurality
of second polymer streams in an alternating fashion to form a
plurality of discrete, alternating layers; and using a
multiplication die, increasing a number of the alternating layers
to form a multilayer composite material, each layer of the
multilayer composite material having a thickness in a range of
about 10 nm to about 0.5 mm.
[0031] These and other features and advantages of the present
application will become apparent from the following detailed
description taken together with the accompanying drawings. It
should be understood, however, that the detailed description and
the specific examples, while indicating preferred embodiments of
the application, are given by way of illustration only, since
various changes and modifications within the spirit and scope of
the application will become apparent to those skilled in the art
from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] For a better understanding of the various embodiments
described herein, and to show more clearly how these various
embodiments may be carried into effect, reference will be made, by
way of example, to the accompanying drawings which show at least
one example embodiment, and which are now described. The drawings
are not intended to limit the scope of the teachings described
herein.
[0033] FIG. 1A is a schematic diagram showing different zones in a
combustion process, including but not limited to the local
degradation zone, the char (or post pyrolysis zone) and the
combustion zone.
[0034] FIG. 1B is a schematic diagram showing a surface flame
advancement process.
[0035] FIG. 2 is a schematic diagram showing a multilayer composite
material according to at least one embodiment described herein.
[0036] FIG. 3A is a schematic diagram showing a UL94 fire test
set-up.
[0037] FIG. 3B shows images of a representative UL94 fire test for
PE/PP/2560 taken at 10 s time intervals.
[0038] FIG. 4A shows scanning electron microscope (SEM; electron
back-scattered for the stained samples; several images combined)
image of 640-layer PE/PP film.
[0039] FIG. 4B shows a TEM image of a first region of a nominal
2560-layer PE/PP film.
[0040] FIG. 4C shows a TEM image of a second region of a nominal
2560-layer PE/PP film.
[0041] FIG. 5A is a graph showing a number of drips normalized by
film thickness for PE and PP films as a function of film
thickness.
[0042] FIG. 5B is a graph showing normalized first drip time as a
function of film thickness for PE and PP samples.
[0043] FIG. 6A is a graph showing linear burning rate as a function
of the inverse of thickness. The dashed line shows the theoretical
values calculated using the parameters listed in Table 2,
below.
[0044] FIG. 6B is a graph showing volumetric burning rate as a
function of the inverse of thickness.
[0045] FIG. 7A is a graph showing first drip time normalized by
film thickness.
[0046] FIG. 7B is a graph showing a number of drips normalized by
film thickness for blends of PE and PP with different contents of
PTFE.
[0047] FIG. 8A is a graph showing first drip time normalized by
film thickness.
[0048] FIG. 8B is a graph showing a number of drips normalized by
film thickness for samples of PE and PP with different structures
(blend and layered).
[0049] FIG. 9A is a graph showing first drip time normalized by
film thickness.
[0050] FIG. 9B is a graph showing a number of drips normalized by
film thickness for layered samples of PE and PP with different
numbers of layers (unannealed vs. annealed (A)).
[0051] FIG. 10 is a fire safety map based on burning rate and
dripping index for different morphologies and materials.
[0052] FIG. 11 is a graph showing volumetric burning rate for
blends of PE and PP with different contents of PTFE.
[0053] FIG. 12 is a graph showing volumetric burning rate for
samples of PE and PP with different structures (blend and
layered).
[0054] FIG. 13 is a graph showing volumetric burning rate for
layered samples of PE and PP with different number of layers
(unannealed vs. annealed).
[0055] Further aspects and features of the example embodiments
described herein will appear from the following description taken
together with the accompanying drawings.
DESCRIPTION OF EXAMPLE EMBODIMENTS
[0056] Various apparatuses, methods and compositions are described
below to provide an example of at least one embodiment of the
claimed subject matter. No embodiment described below limits any
claimed subject matter and any claimed subject matter may cover
apparatuses and methods that differ from those described below. The
claimed subject matter are not limited to apparatuses, methods and
compositions having all of the features of any one apparatus,
method or composition described below or to features common to
multiple or all of the apparatuses, methods or compositions
described below. It is possible that an apparatus, method or
composition described below is not an embodiment of any claimed
subject matter. Any subject matter that is disclosed in an
apparatus, method or composition described herein that is not
claimed in this document may be the subject matter of another
protective instrument, for example, a continuing patent
application, and the applicant(s), inventor(s) and/or owner(s) do
not intend to abandon, disclaim, or dedicate to the public any such
invention by its disclosure in this document.
[0057] Furthermore, it will be appreciated that for simplicity and
clarity of illustration, where considered appropriate, reference
numerals may be repeated among the figures to indicate
corresponding or analogous elements. In addition, numerous specific
details are set forth in order to provide a thorough understanding
of the example embodiments described herein. However, it will be
understood by those of ordinary skill in the art that the example
embodiments described herein may be practiced without these
specific details. In other instances, well-known methods,
procedures, and components have not been described in detail so as
not to obscure the example embodiments described herein. Also, the
description is not to be considered as limiting the scope of the
example embodiments described herein.
[0058] It should be noted that terms of degree such as
"substantially", "about" and "approximately" as used herein mean a
reasonable amount of deviation of the modified term such that the
end result is not significantly changed. These terms of degree
should be construed as including a deviation of the modified term,
such as 1%, 2%, 5%, or 10%, for example, if this deviation does not
negate the meaning of the term it modifies.
[0059] Furthermore, the recitation of any numerical ranges by
endpoints herein includes all numbers and fractions subsumed within
that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.90, 4, and
5). It is also to be understood that all numbers and fractions
thereof are presumed to be modified by the term "about" which means
a variation up to a certain amount of the number to which reference
is being made, such as 1%, 2%, 5%, or 10%, for example, if the end
result is not significantly changed.
[0060] It should also be noted that, as used herein, the wording
"and/or" is intended to represent an inclusive-or. That is, "X
and/or Y" is intended to mean X, Y or X and Y, for example. As a
further example, "X, Y, and/or Z" is intended to mean X or Y or Z
or any combination thereof. Also, the expression of A, B and C
means various combinations including A; B; C; A and B; A and C; B
and C; or A, B and C.
[0061] The following description is not intended to limit or define
any claimed or as yet unclaimed subject matter. Subject matter that
may be claimed may reside in any combination or sub-combination of
the elements or process steps disclosed in any part of this
document including its claims and figures. Accordingly, it will be
appreciated by a person skilled in the art that an apparatus,
system or method disclosed in accordance with the teachings herein
may embody any one or more of the features contained herein and
that the features may be used in any particular combination or
sub-combination that is physically feasible and realizable for its
intended purpose.
[0062] Recently, there has been a growing interest in developing
new technologies that increase the fire safety of polymers. These
technologies may include the avoidance of additives, such as but
not limited to environmentally dangerous additives, that may become
toxic upon combusting.
[0063] Combustion is a phenomenon that combines ignition,
heat-transfer, fluid flow and chemical reaction kinetics. Studies
have shown that flame spread in polymers is usually a
two-dimensional phenomenon that begins with a brief period of
laminar flow followed by progression to turbulent behavior. The
combustion reaction takes place by heating, pyrolysis, ignition,
flame spread, and fire development. FIG. 1A shows different zones
in a combustion process, including but not limited to the local
degradation zone, the char (or post pyrolysis zone) and the
combustion zone.
[0064] Once the polymeric material is ignited, there is a cycle of
processes that occur and cause the flame to spread. These processes
include the heat transfer between the flame and solid material,
degradation and gasification of the solid material, release of
volatile gases, and combustion of the volatile gases.
[0065] Dripping in the combustion process of polymeric materials is
due to the capillary breakup of the stream of melted polymer that
forms behind the flame front.
[0066] Herein, multilayer composite materials, such as multilayer
polymer films, are described. The multilayer composite materials
generally show improvement, for example reduced, response in a
combustion process. For instance, the multilayer composite
materials described herein generally offer reduced dripping and//or
reduced flame spread rates relative to non-layered composite
materials.
[0067] The multilayer composite materials provided herein are
composite materials that include multiple different layers. For
example, the composite materials described herein may include at
least two layers. In at least one embodiment, the composite
materials described herein include at least three layers. In at
least one embodiment, the composite materials described herein
include more than three layers. For instance, in at least one
embodiment, the composite materials described herein include or
more than 10 layers, or more than about 100 layers, or more than
about 500 layers, or more than about 1500 layers, or more than
about 2500 layers.
[0068] In at least one embodiment, the multilayer composite
materials described herein include about 512 layers, or about 640
layers. In at least one embodiment, the composite materials
described herein include about 1520 layers, or about 2560
layers.
[0069] In at least one embodiment, the composite materials
described herein comprise multiple layers of a same material. In at
least one embodiment, the composite materials described herein
comprise one or more layers of different materials. In at least one
embodiment, the composite materials described herein comprise one
or more layers of two different materials, or more than two
different materials. In at least one embodiment, the composite
materials described herein comprise a plurality of layers of two
different materials, each material forming alternating layers with
the other material.
[0070] For example, as shown in FIG. 2, a multilayer composite
material 100 may comprise a first layer 10 and a second layer 20.
The first layer 10 of multilayer composite 100 may comprise a
nonwoven material, as described herein, which may char when burned
and/or exposed to heat and/or flame. The first layer 10 may include
a surface 12 that is an outer layer of the composite 100. The
second layer 20 may also comprise a nonwoven material, as described
herein, which may char when burned and/or exposed to heat and/or
flame. The second layer 20 is generally not adhered to the first
layer 10 by any compound and/or adhesive. The second layer 20 may
include a surface 14 that is also an outer layer of the composite
100.
[0071] In at least one embodiment, the first nonwoven layer and the
second non-woven layer may each be continuous layers.
[0072] Herein, the non-woven layers may include synthetic
materials, such as but not limited to polymer materials, thereby
forming polymer layers. The polymer layers of the multilayer
composite materials described herein may include, but are not
limited to including, one or more polyolefins such as but not
limited to polyethylene (PE) and/or polypropylene (PP). For
example, the polymer layers may include but are not limited to, one
or more of ethylene vinyl alcohol (EVOH), nylon (e.g., nylon 6
and/or nylon 6,6), polyolefins (e.g., polypropylene (PP)),
polyethylene (PE) (e.g., polyethylene high density and/or
polyethylene low density), polyvinylidene chloride (PVDC) (e.g.,
Saranex.RTM.), polyvinylfluoride (PVF) (e.g., Tedlar.RTM.),
acrylic, acrylonitrile rubber, butyl rubber, chlorosulfonated
polyethylene (e.g., Hypalon.RTM.), ethylene chlorotrifluoroethylene
copolymer (ECTFE) (e.g., Halar.RTM.), ethylene propylene diene
monomer (M-class) rubber-coatings (EPDM rubber), fluorinated
ethylene propylene (FEP), fluoro-elastomer polymers (e.g.,
Viton.RTM.), liquid crystal polymers, metal foils, natural rubber,
neoprene, perfluoroalkoxy copolymer (e.g., Teflon.RTM. PFA),
polimide, polyimide-imide (e.g., Tecator.RTM. and Torlon.RTM.),
polyamides, polyesters (e.g., Mylar.RTM.), polyether sulfone,
polyetheretherketone (PEEK, e.g., Victrex.RTM.), polyetherimide,
polymeric coatings, polyphenylsulfone (PPS), polysulfone,
polytetrafluoroethylene (PTFE) (e.g., Teflon.RTM.), polyurethane,
polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) (e.g.,
Kynar.RTM.) poylvinyl choride-acetate (PCA), styrene butadiene
rubber (SBR), polylactic acid (PLA), Polyhydroxyalkanoates (PHA's),
polyglycolic acid (PGA), nylons (e.g. nylon 6,6, nylon 6, and
nylon-MXDs), polyesters (e.g. polycaprolactone (PCL), polyethylene
terephthalate (PET, PETE)), natural polymers (e.g. lignocellulosic
polymers) vacuum metallized films, extrudable polymers that are
used for chemical barrier films in the market place, and/or any
variation, combination and/or hybridization thereof.
[0073] In at least one embodiment, the layers of the multilayer
composite materials described herein include one or more of PEEK,
polyethylene, polyolefin, ECTFE, PVF, nylon, EVA, EVOH,
polypropylene, polyester, and/or ethylene-vinyl chloride
(EVCL).
[0074] In at least one embodiment, the multilayer composite
materials are polymer films having a first layer comprising a first
polymer material and a second layer comprising a second polymer
material. The multilayer composite material may include a plurality
of first layers and a plurality of second layers. The plurality of
first layers may be arranged in any manner and the plurality of
second layers may be arranged in any manner. For instance, the
plurality of first layers may be stacked upon each other and the
plurality of second layers may be stacked upon each other. In
another example, the plurality of first layers may be dispersed
within the plurality of second layers (e.g. alternating with).
[0075] In at least one embodiment, the multilayer composite
materials are polymer films having first, second and third layers,
each layer comprising s different polymer material. Again, the
plurality of first, second and third layers may be arranged in any
manner.
[0076] In at least one embodiment, the multilayer composite
materials are polymer films having first, second, third and fourth
layers, each layer comprising s different polymer material. Again,
the plurality of first, second, third and fourth layers may be
arranged in any manner.
[0077] In at least one embodiment, the multilayer composite
materials are polymer films having alternating layers of
polyethylene (PE) (mIE) and isotactic polypropylene (PP)
(MR10).
[0078] In at least one embodiment, the multilayer composite
materials are polymer films having alternating layers of
polyethylene (mIE) and isotactic polypropylene (MR10) and are
formed by co-extrusion using multiplier slit dies.
[0079] In at least one embodiment, the multilayer composite
materials are polymer films having alternating layers of
polyethylene (mIE) and isotactic polypropylene (MR10) and are
formed by co-extrusion using multiplier slit dies.
[0080] Generally, the composite materials described herein are free
of any flame retardants additives. For instance, a flame retardant
additive is a non-polymeric additive or blend of additives used to
impart or increase flame resistance properties of an article or
material.
[0081] In at least one embodiment, the morphology (i.e. the
arrangement and/or relative size of the layers) of the composite
materials described herein provide at least two physical phenomenon
close to the combustion zone when the composite materials are
heated. First, in at least one embodiment, the morphology of the
composite layers provides for individual layers to thicken in the
combustion zone which is an indicator of retraction of the
individual layers. Retraction of the individual layers can delay
the onset of drips and reduce the number of drips of the composite
materials.
[0082] Secondly, reduction in normalized drip numbers of the
composite materials described herein can also be attributed to the
morphology of the composite materials described herein providing
for each layer to undergo an increase in extensional viscosity. In
at least one embodiment, the number of layers of the composite
material may provide for an increase of the extensional viscosity
of the composite material, for example in an area close to the
combustion zone.
[0083] In at least one embodiment, methods of forming composite
materials, including but not limited to multilayer composite
materials are described herein.
[0084] In at least one embodiment, the multilayer composite
materials described herein are formed in a coextrusion process
using multiplier slit dies. The details of the process have been
described elsewhere..sup.33
[0085] For example, in at least one embodiment, PE/PP multilayers
can be formed by, using a first (e.g. a single screw or a twin
screw) extruder, feeding PE to one or more dies while also, using a
second (e.g. a single screw or a twin-screw extruder) extruder,
feeding PP to the same dies. Each extruder may be connected to a
gear pump to control the volumetric flow rate and overall film
composition.
[0086] After being extruded from one of the extruders, the molten
polymer streams are delivered to a feedblock to split each stream
into a plurality of streams. For example, each stream may be split
into 10 streams. These streams are then combined in an alternating
fashion to form a plurality of discrete, alternating layers. For
example, in the event that the feedback splits each stream in to 10
streams, the two groups of 10 streams may be combined in an
alternating fashion to form 20 discrete layers.
[0087] One or more (e.g. a series) of multiplication dies may be
used to split each incoming stream into two identical streams that
can be stacked on top of one another, so that each multiplying die
doubled the number of layers. In one example, five multipliers may
be used to manufacture composite materials comprising about
640-layer films. In another example, seven multipliers may be used
to manufacture composite materials comprising about 2560-layer
films. The skilled person will understand that other amounts of
layers may be formed by splitting the molten polymer streams into a
different number of split streams and/or subsequently using
different multiplication dies.
Examples
[0088] In one example, linear low-density PE and two grades of PP
were used to investigate the effects of multilayer versus blend
morphology on dripping and burning rates in polymeric films. Also,
polytetrafluoroethylene (PTFE) additives, polystyrene (PS), and
commercial DuPont Tyvek.RTM. home wrap were obtained for
establishing a reliable benchmark for the investigation.
TABLE-US-00001 TABLE 1 Polymers used for this study. Density
(25.degree. C.), Melt Flow Index Melt Flow Index .rho. (190.degree.
C./2.16 kg) (230.degree. C./2.16 kg) Polymer Manufacturer Grade
name [g/cm.sup.3] [g/10 min] [g/10 min] PE Total Lumicene 0.918 3.5
-- M1835 PP Total Lumicene 0.902 -- 10 MR10MM0 PTFE Daikin
Chemicals Polyflon MPA 0.45 -- -- FA-5601 PP' RTP Company RTP100
0.91 -- 4 PS Americas STYRON 666D 1.04 8 (@ 200.degree. C./5 kg) --
Styrenics LLC
Materials
[0089] Table 1 lists the polymers used in this example along with
information about their density and melt flow indices. Polymers
were used as received from suppliers. Pairs of PE and PP were used
to prepare blends and the multilayered structures with nominally
640 and 2560 layers at a 50/50 volume composition. Also, 50/50 melt
blends of the PE/PP pair with up to 2% wt. of PTFE were
prepared.
[0090] PTFE (Polyflon MPA FA-5601) powders were acquired from
Daikin Industries, Ltd. and used as anti-dripping agents. The bulk
density of the powders was 0.45 g/mL and their average particle
size was 0.5 mm. Also, PS and DuPont.TM. Tyvek.RTM. HomeWrap.RTM.,
a commercially available product, were obtained and used as
received.
Multilayer Film Fabrication
[0091] Multilayer film samples were prepared in a coextrusion
process using multiplier slit dies. The details of the process have
been described elsewhere..sup.33 In the PE/PP multilayers, a single
screw extruder (25 mm diameter, Killion) fed PE to the dies while a
twin-screw extruder (16 mm diameter, Prism TSE 16TC) delivered PP
to the dies. Each extruder was connected to a gear pump to control
the volumetric flow rate and overall film composition. Then, the
molten polymer streams were delivered to a feedblock that split
each stream into 10 streams. These streams were combined in an
alternating fashion to form 20 discrete layers. A series of five
multiplication dies were used to split each incoming stream into
two identical streams that were stacked on top of one another so
that each multiplying die doubled the number of layers. Five
multipliers were used to manufacture nominally 640-layer films;
seven multipliers were used to manufacture the nominally 2560-layer
films. A fishtail die was used to fabricate each film with a final
cross-section of 22.times.0.8 mm. The temperatures of all parts
were set and controlled at 200.degree. C. The fabricated films were
quenched on counter-rotating chill rolls with temperatures at
90.degree. C. before winding up on a spool. The overall thickness
for the prepared films after cooling was controlled to be between
0.1 and 0.7 mm by adjusting the speed of the chill rolls. The range
of thicknesses provided for investigation of the impact of
thickness on dripping and burning rates of the produced films.
Layered PE/PP samples were annealed to investigate the influence of
annealing on dripping and burning rates in the films. Annealing
took place for 2 min at 180.degree. C. The samples were quenched
after annealing using cold plates at 90.degree. C. The films were
characterized by SEM and TEM as described below.
Blend Film Fabrication
[0092] Blends of PE/PP were prepared using a Haake batch mixer at a
set temperature of 180.degree. C. and a rotor speed of 150 rpm. The
mixed samples were removed from the internal mixer after 600 s.
Blend films were produced by hot press compression (Carver Press).
The samples were heated up to 180.degree. C. for 60 s and then
pressed under 8900 N for the duration of 60 s. Spacers were used to
make films with thicknesses ranging from 0.1 to 0.7 mm. Also,
several PS films were produced by hot pressing under the same
conditions.
[0093] The notation used herein, e.g., PE/PP/640A, refers to the
materials in the films followed by the nominal number of layers,
based on ideal multilayer coextrusion. Letter "A" refers to the
multilayer samples that were annealed. Letter "B" refers to the
blends. For the samples containing PTFE, the number following
"PTFE" is the weight percentage of the additive.
Fire Test Measurements
[0094] Dripping and burning rates were measured following the
procedure specified by the UL94 vertical flame test, which is
illustrated in FIG. 3A. The UL-94 flame test is the most general
standard for plastic products. A Bunsen burner with a 20 mm flame
height was placed underneath the specimens. The samples,
125.times.30 mm, were clamped between aluminum frames using two
clips and experiments were performed inside an aluminum frame under
a fume hood. Use of the frame limited perturbation of the airflow
around the sample. Sample burning was recorded using a Canon Rebel
T3i high definition camera up to the point where the flame passed
the 125 mm mark line. Film footage was manually analyzed to
determine the burning rate, first drip time, and the total number
of drips. Experiments were repeated three times for each sample. On
each of the following figures, the range of data points has been
shown with a box while the line in the middle of the box is the
median of the data set, and the "x" within the box is the mean of
the data set of three measurements. Images of a representative
burning sample obtained at 10 s time intervals are shown in FIG.
3B.
Layered Structure
[0095] Film morphology was investigated to quantify the number of
layers present in each multilayer film. FIG. 4 shows representative
SEM and TEM images obtained from the nominally 640-layer and
2560-layer PE/PP films. The images show that continuous, discrete
layered structures are present in the films although the number of
layers is less than the nominal number of layers. The actual number
of layers for PE/PP/640 and PE/PP/2560 is estimated to be around
512 and 1520, respectively. The lower number of layers is due to
layer breakup that happens in the multiplying die blocks. In
labeling the samples, the nominal numbers were retained.
Effect of Material Thickness on Dripping and Burning Rates
[0096] Polymeric films were fabricated in varying thicknesses. To
investigate the effect of thickness on dripping and burning rates,
samples of homopolymers with different thicknesses were prepared.
FIG. 5A presents the number of drips normalized by film thickness
for PE and PP samples. The average value of all data points,
corresponding to 1730 drips/mm with the standard deviation of 510
drips/mm, has been marked as a dashed line in FIG. 5A. It can be
seen that the normalized values are clustered around the average
value line, showing almost no dependency on film thickness within
experimental error. As the thickness of the film changes, the
volume of the samples changes accordingly since the other two
dimensions are fixed according to the UL94 fire test standard. The
consistent clustering of the normalized values around the average,
independent of film thickness, can be attributed to the
proportionality between the mass of the sample and the number of
drips. It can be inferred that regardless of the sample volume, the
size of the drips is almost constant. Also, PE and PP show
comparable numbers of normalized drips.
[0097] FIG. 5B shows the first drip times normalized by film
thickness as a function of film thickness. Analogous to drip
numbers, first drip times have a relationship with thickness. The
dashed line in FIG. 5B shows the average value for the normalized
first drip times of PE and PP films, corresponding to 15 s/mm with
a standard deviation of 6 s/mm. Although the standard deviation is
large, there is no trend, and the experimental values are clustered
around the average value line and the normalized first drip times
are independent of film thickness within experimental errors. The
gravity forces can be equated with the resistance of a viscous
droplet at the pinch-off time for slow extensional rates. Pinch-off
time (here first drip time), t*, can be estimated as shown below in
Eq. (1):
t * .times. .about. .times. .eta. E .rho. .times. g .times. r c
.times. r 2 .times. h 0 ( 1 ) ##EQU00001##
[0098] where .eta..sub.E is the extensional viscosity, .rho. is the
density, g is the acceleration of gravity, h.sub.0 is the sample
thickness, and r.sub.cr is the critical radius at which the droplet
disengages from the melt stream. Extensional viscosity acts as a
resistance against droplet falling and delays the first drip time.
As the extensional viscosities for PE and PP samples are
similar,.sup.34 the first drip times for these samples agree within
the experimental error. According to Eq. (1), the thicker the
sample is, the longer it takes for droplet disengagement from the
stream of fluid. Hence, normalizing the number of drips and first
drip time to sample thickness permits quantitative comparisons
between samples with different thicknesses.
[0099] Sample thickness plays additional roles in the burning rates
of polymers. The effect of thickness on the linear burning rates
for PP and PE samples is illustrated in 6A, where the linear
burning rates were calculated by determining the time required for
the flame to reach the 125 mm mark line (see FIG. 3). In studies
that deal with burning rate, materials are usually grouped into two
categories: (i) thermally thin materials with Biot numbers less
than 1, and (ii) thermally thick films with Biot numbers greater
than 1 mm..sup.3,35 In thermally thin materials, thermal inertia is
negligible and the temperature gradient across the sample can be
neglected.
[0100] Most of the predictions for burning rates have been based on
the simple models developed by de Ris..sup.36 For thermally thick
films with semi-infinite fuel beds, de Ris obtained the linear
burning rate, V, as,.sup.36
V .apprxeq. q . f 2 .times. .delta. f k .times. .rho. .times. C p
.function. ( T p - T .infin. ) 2 ( 2 ) ##EQU00002##
while for thermally thin films,
V .apprxeq. 2 .times. k .function. ( T f - T p ) .rho. .times. C p
.times. h 0 .function. ( T p - T .infin. ) ( 3 ) ##EQU00003##
where k is the thermal conductivity of the material, .rho. is the
material density, C.sub.p is the heat capacity, and h.sub.o is the
film thickness. The other parameters are defined in FIG. 1B. The
Biot number is the ratio of the thermal resistance inside the
material to the thermal resistance at the surface. For a film of
0.7 mm thick Bi=0.016 to 0.16, much smaller than 1. Since the
polymeric specimens in this study are thinner than 0.7 mm, they are
safely considered thermally thin and Eq. (3) was used to evaluate
experimental results on burning rates.
[0101] The measured burning rates are in excellent agreement with
the predictions proposed by de Ris in Eq. (3), as shown in FIG. 6A.
These predictions were generated using the values listed in Table
2, which are typical for polyolefins. FIG. 5B shows the volumetric
burning rates of the PE and PP films as a function of the inverse
of thickness, where the values are clustered around an average
value of 1510 mm.sup.3/s with a standard deviation of 180
mm.sup.3/s. This is in great agreement with the estimates of the de
Ris model that predicts the average volumetric burning rates at
1481 mm.sup.3/s.
TABLE-US-00002 TABLE 2 Physical and thermal parameters and
combustion temperatures for typical polyolefins..sup.37 Parameter
Symbol Unit Polyolefins Heat capacity C.sub.p J/kg K 2000 Melt
Density .rho. kg/m.sup.3 800 Thermal conductivity k W/m K 0.22
Flame temperature T.sub.f K 2265 Pyrolysis temperature T.sub.p K
670 Ambient temperature T.sub..infin. K 293
Effect of PTFE Additive on Dripping
[0102] PTFE is commonly used as anti-dripping and flame-retardant
agents for polymeric materials. Although there are acute human
health and environmental concerns around halogenated additives
including PTFE,.sup.24,25,38 the study was extended to PE/PP
samples containing PTFE to establish a benchmark for the
performance of the fabricated layered structures. FIG. 7A exhibits
the normalized first drip time for the samples with and without
PTFE additives. The addition of PTFE to the PE/PP blends increased
the first drip times almost two-fold, from 11 s/mm for the PE/PP
blends to 20 s/mm for the PE/PP blends containing 2% wt. of PTFE
additive. The first drip times for the PE/PP blends containing 0.5%
wt. and 1% wt. of PTFE additive were also about 22 s/mm. Thus, the
improvement observed for the first drip time did not depend on the
content of PTFE within the range of 0.5% wt. to 2% wt.
[0103] The normalized number of drips for the samples with and
without PTFE additives are illustrated in FIG. 7B. The addition of
PTFE to the PE/PP blends reduced the normalized number of drips
from 940 drips/mm for the PE/PP blends to 370 drips/mm for blends
with up to 2% wt. of PTFE. PTFE concentration had only a minor
effect on the normalized number of drips which for 0.5% wt. and 1%
wt. of PTFE additive were 413 drips/mm and 374 drips/mm,
respectively. The reduction in drips has been attributed to the
formation of PTFE fibrils in the blends that increase the
extensional viscosity causing a delay in the first drip time and a
concomitant reduction in the number of drips..sup.39 This
observation is in line with the findings of Kempel et al..sup.40
who reported the efficacy of PTFE in preventing dripping by
increasing the viscosity for polycarbonate/acrylonitrile butadiene
styrene blends. Although PTFE can be a solution to reduce dripping
in polymeric materials, these results show that, despite containing
a halogen, PTFE additives do not provide a significant benefit to
burning rates. In fact, 0.5% PTFE showed a 20% increase in burning
rate (see FIG. 11).
Effect of Layered Structure on Dripping
[0104] After investigating the effect of thickness and
understanding the influence of anti-dripping agents on dripping,
samples with 640 and 2560 layers were investigated as extruded and
after annealing to understand the effect of the layered structure
on dripping. FIG. 8A depicts the normalized first drip times
obtained for the PE and PP homopolymers, a 50/50 blend, and the
layered PE/PP samples. Melt blended PE/PP films had a normalized
first drip time of 11 s/mm, which was within the experimental error
of the average normalized first drip times of the corresponding
homopolymers, 14 s/mm. The normalized first drip time for
coextruded multilayer films was significantly delayed in
comparison, with PE/PP/640 at 36 s/mm; a 141% increase compared to
melt blended PE/PP. This value for PE/PP/2560 was 37 s/mm, a 154%
increase relative to the normalized first drip times of the melt
blended PE/PP. Considering the experimental error, this increase
from 640 layers to 2560 layers is not statistically significant.
From the comparison of the values for PE/PP/640 and PE/PP/2560 with
the PTFE filled samples (shown in FIG. 7), it can be inferred that
the layered structure has a greater impact on delaying the first
drip time although PTFE additives are extensively used as
anti-dripping agents in the industry.
[0105] Besides the first drip time, the overall number of drips was
also influenced by the different morphologies. As shown in FIG. 8B,
the number of drips for the blends was 940 drips/mm, a reduction of
49% compared to the average value for the homopolymers of 1840
drips/mm. This result contrasts with the first drip time where
there was little difference between blends and the homopolymers.
For the multilayer samples, the normalized number of drips improved
over 80% compared to PE/PP blends, reducing to 190 drips/mm and 120
drips/mm for PE/PP/640 and PE/PP/2560, respectively. The normalized
number of drips for the PE/PP/640 and PE/PP/2560 samples were
noticeably less than what was obtained for the PTFE filled blends
(370 drips/mm). This finding shows the efficacy of the layered
structure in reducing the drip numbers of PE and PP samples and
suggests that layered structures could be an additive-free
alternative to conventional anti-dripping agents. However, these
results show that layered structures do not provide any benefit for
burning rate relative to the PE/PP blends (see FIG. 12).
[0106] To better understand how multilayer coextrusion contributes
to dripping behavior and burning rates in PE/PP films, the
multilayer samples were annealed. Understanding the impact
annealing has on dripping and burning rate can be important as
several polymer processing techniques feature secondary processes
where polymers are exposed to higher temperatures after primary
production processes. These experimental results showed that
annealing the samples reduced the delay to the time of the first
drop (FIG. 9A). The normalized first drip times for the annealed
PE/PP samples with 640 and 2560 layers were 14 and 16 s/mm,
respectively, showing significant drops of 62% and 57%, compared to
the corresponding unannealed samples with normalized first drip
times of 36 and 37 s/mm. The normalized first drip times for the
annealed specimens were close to the normalized first drip time of
the PE/PP blends (11 s/mm).
[0107] FIG. 9B shows the number of drips for the annealed samples
adjacent to their corresponding unannealed controls. The normalized
drip numbers for the PE/PP multilayer films with 640 and 2560
layers after annealing were 330 and 610 drips/mm, respectively.
These values represent increases of 71% and 412% compared to the
values for their corresponding unannealed specimens (190 and 120
drips/mm). The measured values for the annealed samples had
intermediate values between the data for the layered PE/PP samples
and the PE/PP blends with the normalized drip number of 940
drips/mm. The change in the drip numbers was much more noticeable
for the multilayer samples with 2560 layers compared to the samples
with 640 layers.
[0108] To investigate the structural changes that might lead to the
observed differences, TEM images of the samples in areas close to
the combustion zone (shown in FIG. 1A) were obtained. This was done
after burning the samples for 3-5 s then extinguishing the flame.
Samples for TEM were cut 5-10 mm from the burned edge of the
samples. TEM images of the layered samples after annealing were
also captured. The images were in good agreement with the
regularity of the layers shown in FIG. 4. Further, the thicknesses
of layers, stacked from bottom left to top right, appeared to be
somewhat thicker, which might be due to a reduced resolution by
using unstained sample slices with weak electron density
contrast.
[0109] The blend samples showed highly extended PE droplets. These
were formed during mixing and stretching during the compression
molding used to fabricate films. The morphology of the blend sample
close to the combustion zone was also imaged and showed contraction
and breakup of the extended PE phase in the PP matrix. This droplet
retraction likely contributed to the reduction in the normalized
number of drips for the blend samples compared to the pure PE and
PP samples. Retraction appeared to have taken place due to
interfacial tension acting on the droplets and recovery from
molded-in stresses as temperatures increase above the melting
points of the polymers during burning.
[0110] The morphology of a 640-layer sample close to the combustion
zone was also imaged. The layers were thicker than other images,
indicating retraction of the sample which delayed the onset of
drips and reduced the number of drips. The reduction in normalized
drip numbers can also be attributed to higher extensional
viscosity. Jordan et al..sup.34 measured extensional viscosity on
coextruded films of these same polymers. They found that the number
of layers directly increased the extensional viscosity of PE/PP
multilayers. Thus the 2560-layer sample is predicted to have even a
higher extensional viscosity. In the area close to the combustion
zone, layers of the 2560-layer sample, stacked from bottom right to
top left, were thicker and had retracted enough to start breaking
up. This combination of layer breakup (or coarsening) and increased
extensional viscosity for the 2560-layer samples may have been the
cause for the long time to first drip and the normalized drip
numbers being even lower than for the 640-layer sample.
[0111] The morphology of the 640-layer and 2560-layer samples after
annealing were also imaged. These images were similar to those
taken close to the combustion zone. In a sense, the retraction
during quiescent annealing "wastes" the potential to reduce
dripping during burning and thus both samples show more dripping
after annealing. The 2560-layer sample showed a bigger increase in
drips/second over its original value due to the greater coarsening
and drop breakup.
Fire Safety Map
[0112] There are a plethora of studies that have focused on the
quantitative determination of burning rates for materials, but
these investigations largely ignore the first drip time and overall
drip numbers..sup.1,3,48,49 Many fire safety classifications are
qualitative and only based on the ignition of materials and
flammability of the drips, neglecting the contributions of first
drip time and overall drip numbers to consumer safety..sup.25,50
There is a need for a method to select materials based on
collective performance in fire tests. To accomplish this, a
quantitative parameter called the "dripping index" (DI) was defined
that combines the parameters of the first drip time and drip
numbers into a general behavior. DI is defined as the ratio of the
drip numbers per unit volume to the first drip time per film
thickness,
DI = Drip .times. .times. number .times. .times. per .times.
.times. unit .times. .times. volume First .times. .times. drip
.times. .times. time .times. .times. per .times. .times. unit
.times. .times. thickness ##EQU00004##
[0113] DI is a simple, yet practical and effective combined
parameter that accounts for the severity of the dripping behavior.
This definition also provides for ruling out the volume and
thickness effects, making DI applicable to many fire testing
standards and experiments. It provides for making comparisons of
the flammability of the layered materials to standard polymers. As
the dripping index increases, one might expect a higher number of
drips and/or shorter times required for the first drip, both
signaling enhanced fire spreading behavior. Lower values of DI are
indicative of samples that feature fewer drips and/or a delayed
drip time during the combustion process, meaning a lower propensity
for fire spread. The dripping index along with the volumetric
burning rates was then used to establish a map for fire safety of
the studied materials with varying morphologies. This map, depicted
in FIG. 10, can be used as a quantitative robust criterion for
material selection, augmenting the current fire safety standards
which ignore the number of drips and time to the first drip. The
goal of the fire safety map is to select polymeric materials that
lie in the lower left region and also do not generate toxic fumes
in burning.
[0114] In FIG. 10, data for polystyrene (PS) is included, another
grade of polypropylene (PP'), and commercially available home wrap
(Tyvek.RTM.) to highlight the usefulness of the fire safety map in
material selection. It is worth mentioning that Tyvek.RTM. is a
nonwoven fabric, while all the other samples in this study
(controls, blends, and layered) are continuous films. Also, some
flame retardants are generally used to coat the surface of home
wrap products and home wraps are significantly more expensive than
films, even multilayer films. While PE and PP homopolymers have
higher dripping indices, the dripping index shows more than one
order of magnitude reduction for layered structures. This may be
attributed to increased extensional viscosities and retraction
processes leading to morphological changes in the layered
structures. Unlike PE and PP films, PS had a lower dripping index
due to soot formation in the combustion process. This demonstrates
the effectiveness of the solid phase char-formation mechanism in
insulating the burning zones from the rest of the polymeric
material. Tyvek.RTM. shows lower values of DI, however, its burning
rate is similar to all the other polymer films. Upon annealing, the
integrity of layered structures changes due to coarsening and layer
breakup. This led to the intermediate behavior of the annealed
films between the corresponding films with layered structures and
blends.
SEM AND TEM Microscopy
[0115] The morphology and the actual number of layers were
determined using SEM and TEM. The coextruded multilayer PE/PP
samples were cryo-microtomed at -120.degree. C. with a glass knife
to expose a smooth edge-on cross-section of the multilayer film.
Each sample was cryo-microtomed at an angle so that the knife marks
were distinguishable from the multilayer structure. The trimmed
multilayer cross-section was exposed to vapors of a ruthenium
tetroxide (RuO.sub.4) solution for 30 min before being dried in a
fume hood overnight. Additional trimming was performed by
cryo-microtome at -120.degree. C. with a glass knife to remove
excess RuO.sub.4 aggregates on the surface. Following the second
trimming, 1.5 nm of iridium was sputter-coated (Leica EM ACE600)
onto the cryo-microtomed surface to prevent charging during SEM
(Hitachi SU8230) imaging. The SEM instrument was equipped with a
cold field emission gun and the SEM images were obtained with an
accelerating voltage of 25 kV. The multilayer structure was
observed with a back-scattered electron detector (BSE) where the PE
layers are distinguished as bright and dark domains. To span the
entire sample at the resolution needed to measure layer thicknesses
with sub-micron dimensions, six to nine separate high-magnification
micrographs were manually stitched together. For TEM measurements,
cross sections of the PE/PP films (thickness: ca. 70-100 nm) were
prepared by cryomicrotoming at -140.degree. C. using a Leica EM UC6
Ultramicrotome equipped with cryogenic chamber. A Diatome diamond
knife was used to cut the slices that were transferred to TEM grids
using saturated sucrose solution. A perfect loop (Electron
Microscopy Sciences, Hatfield, Pa.) was also utilized. The images
were obtained using a Tecnai G2 Spirit BioTwin microscope with an
accelerating voltage of 120 kV. The TEM images for morphology
change after burning or annealing were obtained with unstained
samples (thickness: ca. 70-100 nm) microtomed at room temperature
using a Leica EM UC7 Ultramicrotome. A Talos L120C TEM
(accelerating voltage of 120 kV) was used.
Effect of PTFE Additive on Burning Rates
[0116] FIG. 11 shows the burning rate for the PE/PP films with and
without PTFE additives. The burning rate for films with 0.5% wt.
PTFE was 2130 mm.sup.3/min. This value shows a 20% increase
compared to the burning rate of 1770 mm.sup.3/min for the PE/PP
blends with no PTFE. The burning rates for the samples containing
1% wt. and 2% wt. of PTFE additives are 1949 and 1650 mm.sup.3/min,
respectively. The PTFE filled samples showed no significant
benefits for burning rates of samples.
Effect of Layered Structure on Burning Rates
[0117] Although the multilayer structure showed a huge impact on
dripping of PE and PP films, it showed no benefit in terms of
burning rates. FIG. 12 illustrates the results for the volumetric
burning rates in the PE/PP films for different morphologies. Melt
blended PE/PP films show an increase in burning rate, 1770
mm.sup.3/min, compared to the homopolymer samples of PE and PP,
1444 and 1640 mm.sup.3/min, respectively. This is equal to 230
mm.sup.3/min increase (slightly greater than the standard deviation
for the PE and PP homopolymers in FIG. 7B) compared to the average
value for two homopolymer samples, i.e. 1540 mm.sup.3/min. The
PE/PP films with 640 layers had burning rate values of 1720
mm.sup.3/min, which is within experimental error for the average PE
and PP burning rates. More noticeably was the burning rate for the
specimens with 2560 layers, which is 2550 mm.sup.3/min. This value
is higher than the burning rates of the other morphologies. The
increase in the burning rates can be associated with retraction of
layered conformations due to the residual stresses present in the
structure of the films. Retraction facilitates the upward movement
of the specimen, and hence, the flame in the vertical direction,
leading to faster burning rates.sup.51,52. The greater aspect ratio
of the formed layers reveals greater retraction
capability.sup.53-55, contributing to higher burning rate values
observed for the films with a higher number of layers. Also, this
finding reveals the limitation of the UL94 standard that does not
quantitatively describe the dripping behavior of samples. Based on
the UL94 fire standard, the dripping behavior is defined based on
the presence of dripping for specimens, and either the drips are
flaming or not.sup.56. Without a quantitative measure, one might
neglect the advantages of the layered structures in terms of
dripping as one of the important fire safety parameters.
[0118] FIG. 13 shows burning rates obtained for the multilayer
films next to the values determined for the corresponding annealed
samples. As shown, the burning rates of the samples did not show
noticeable changes with annealing for 2 min at 180.degree. C. It
can be inferred that the retraction processes are still present for
the annealed 2560 samples which facilitate the upward movement of
the film and flame.
[0119] While the applicant's teachings described herein are in
conjunction with various embodiments for illustrative purposes, it
is not intended that the applicant's teachings be limited to such
embodiments as the embodiments described herein are intended to be
examples. On the contrary, the applicant's teachings described and
illustrated herein encompass various alternatives, modifications,
and equivalents, without departing from the embodiments described
herein, the general scope of which is defined in the appended
claims.
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